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CN-122024579-A - Anti-counterfeiting label based on laser-induced perovskite quantum dot microarray and preparation method thereof

CN122024579ACN 122024579 ACN122024579 ACN 122024579ACN-122024579-A

Abstract

The invention relates to the technical field of anti-counterfeit labels, in particular to an anti-counterfeit label based on a laser-induced perovskite quantum dot microarray and a preparation method thereof. The perovskite quantum dot micro-array comprises a substrate, a perovskite quantum dot micro-array, a composite micro-nano structure, a flexible transition layer and an ultrathin protective layer, wherein the flexible transition layer covers the surface of the perovskite quantum dot micro-array, the ultrathin protective layer covers the surface of the flexible transition layer, a perovskite quantum dot precursor residual curing layer is arranged between the perovskite quantum dot micro-array and the substrate, the perovskite quantum dot micro-array is of a submicron structure, perovskite quantum dot precursor in-situ crystallization is prepared on the substrate, and the perovskite quantum dot micro-array is formed by perovskite quantum dot partitions with different components. The preparation method realizes the preparation of the submicron-level high-precision perovskite quantum dot anti-counterfeiting label, and has the characteristics of multi-dimensional collaborative anti-counterfeiting, environment irreversible response, degradability, flexible adaptation and the like.

Inventors

  • LIU YUMING
  • Qi Kaihang
  • CHEN DANYANG
  • ZHOU YONG

Assignees

  • 西北工业大学

Dates

Publication Date
20260512
Application Date
20260205

Claims (10)

  1. 1. The anti-counterfeiting label based on the perovskite quantum dot microarray induced by laser is characterized by comprising a substrate, the perovskite quantum dot microarray, a composite micro-nano structure, a flexible transition layer and an ultrathin protective layer; the flexible transition layer covers the surface of the perovskite quantum dot microarray, the ultrathin protective layer covers the surface of the flexible transition layer, a perovskite quantum dot precursor residual curing layer is arranged between the perovskite quantum dot microarray and the substrate; the perovskite quantum dot microarray is of a submicron structure, perovskite quantum dot precursors are prepared on the substrate for in-situ crystallization, and the perovskite quantum dot microarray is formed by perovskite quantum dot partitions with different components; The composite micro-nano structure and the perovskite quantum dot microarray are prepared synchronously to form the deep anti-counterfeiting structure.
  2. 2. The anti-counterfeit label based on the laser-induced perovskite quantum dot microarray, which is disclosed in claim 1, is characterized in that the substrate is a rigid substrate or a flexible substrate, the rigid substrate is one of glass and quartz, and the raw materials comprise, by weight, 10-15% of SiO 2 60~75wt%、Al 2 O 3 , 5-8% of CaO, 2-5% of MgO and 0.3-1.0 mm; the flexible substrate is one of PET and PI, and comprises the following raw materials, by weight, 85-95wt% of polyethylene terephthalate, 1-3wt% of an antioxidant, 2-5wt% of a toughening agent, 1-2wt% of a weather-resistant agent and 0.1-0.3 mm in thickness.
  3. 3. The anti-counterfeiting label based on the perovskite quantum dot microarray induced by laser according to claim 1, wherein the size of the perovskite quantum dot microarray is 50 nm-1 μm, the deviation of unit size is less than or equal to 5%, the edge roughness is less than or equal to 10nm, and the fluorescence quantum yield is more than or equal to 85%; The perovskite quantum dots with different components comprise CsPbCl 3 blue light, 450-480 nm, csPbBr 3 green light, 520-550 nm, csPbI 3 red light, 620-650 nm and mixed component perovskite quantum dot near infrared light, 700-800 nm; The perovskite quantum dots have the components with the molar ratio of Cs + :Pb 2+ :I - =1:1:3 in Cs + :Pb 2 + :Br⁻=1:1:3,CsPbI 3 in Cs + :Pb 2+ :Cl⁻=1:1:3,CsPbBr 3 in CsPbCl 3 , the perovskite quantum dots with the mixed components are any one of CsPbCl 3 -CsPbBr 3 、CsPbBr 3 -CsPbI 3 , and the mixed molar ratio is 1:9-9:1 The fluorescence service life of the perovskite quantum dots of the same component is classified into 0.5ns, 1.5ns, 3ns and 5ns, the service life deviation is less than or equal to 0.05ns, and the fluorescence polarization directions comprise 0 degrees, 90 degrees, 180 degrees and 270 degrees and are accurately matched with the period of the micro-nano grating.
  4. 4. The anti-counterfeiting label based on the laser-induced perovskite quantum dot microarray according to claim 1, wherein the composite micro-nano structure comprises a micro-lens array, a micro-nano grating and a micro-nano password lattice; each microlens corresponds to one perovskite quantum dot microarray unit; the period of the micro-nano grating is 100-500 nm, and the grating periods of different areas are adapted to the fluorescence polarization splitting angles of the corresponding perovskite quantum dots; The micro-nano password lattice is hidden in the gap of the perovskite quantum dot microarray, the size is 50-100 nm, and the arrangement logic is matched with the fluorescence service life and the color of the perovskite quantum dot; The micro-lens array raw material comprises, by mass, 1-3wt% of Si 2 90~95wt%、TiO 2 3~5wt%、ZrO 2 ; The micro-nano grating and micro-nano password lattice raw materials are consistent with the substrate.
  5. 5. The anti-counterfeit label based on the laser-induced perovskite quantum dot microarray according to claim 1, wherein the raw material components and mass fractions of the dual environment-responsive perovskite quantum dot precursor are 30-50wt% of the perovskite quantum dot precursor, 40-60wt% of a solvent, 1-3wt% of a nano-scale dispersing agent, 0.5-2wt% of a crystallization regulator, 1-4wt% of a dual-response group reagent, 2-5wt% of a biocompatible ligand and 0.1-0.5wt% of a rare earth element marker The solvent is one or two of N, N-dimethylformamide and dimethyl sulfoxide, and the mixing volume ratio is 1:1-3:1; The rare earth element marker is any one of Eu 3+ 、Tb 3+ .
  6. 6. The anti-counterfeiting label based on the laser-induced perovskite quantum dot microarray according to claim 1, wherein the flexible transition layer is a PMMA film and has a thickness of 10-20 nm; the ultrathin protective layer is an Al 2 O 3 film with the thickness of 5-10 nm; And the thickness of the residual curing layer of the perovskite quantum dot precursor is 5-15 nm.
  7. 7. A method of preparing a security tag based on a laser-induced perovskite quantum dot microarray according to any one of claims 1 to 6, comprising the steps of: Step 1, preprocessing a substrate, modifying the substrate surface by adopting plasma etching combined with a gradient self-assembled monomolecular film, constructing a hydrophilic-hydrophobic micro-nano gradient structure, and adapting to in-situ crystallization and positioning of a perovskite quantum dot microarray; Step 2, preparing a perovskite quantum dot precursor, sequentially adding the perovskite quantum dot precursor, a solvent, a nano-grade dispersing agent, a crystallization regulator, a double-response group reagent, a biocompatible ligand and a rare earth element marker according to calculated components and proportions, and stirring for 30-60 min at 25-35 ℃ and 300-500 r/min to obtain a uniform and stable perovskite quantum dot precursor; Step 3, synchronously preparing the perovskite quantum dot microarray and the composite micro-nano structure, uniformly coating a perovskite quantum dot precursor on the surface of a substrate, inducing in-situ crystallization of the perovskite quantum dot precursor by adopting a femtosecond laser cold processing technology, preparing the perovskite quantum dot microarray, synchronously preparing the composite micro-nano structure by adopting a double-beam femtosecond laser, and accurately aligning the perovskite quantum dot microarray; step 4, depositing a protective layer, namely depositing a flexible transition layer and an ultrathin protective layer on the surface of the perovskite quantum dot microarray by a vapor deposition method; Step 5, post-treatment, namely drying at room temperature to remove redundant solvent, so that the precursor residual part between the perovskite quantum dot microarray and the substrate is solidified to form a residual solidified layer, and a finished product anti-counterfeit label is obtained; If the flexible anti-counterfeiting label is prepared, a flexible transfer step is added before the step 4, and the perovskite quantum dot microarray and the composite micro-nano structure are transferred to a flexible substrate.
  8. 8. The method for preparing the anti-counterfeit label based on the laser-induced perovskite quantum dot microarray, according to claim 7, wherein in the step 1, the plasma etching power is 40-60W for 5-15 min; The gradient self-assembled monomolecular film is modified for 1-2 hours at 20-30 ℃ by adopting octadecylamine, and the diameter of the hydrophilic core area is matched with the size of the microarray unit.
  9. 9. The preparation method of the anti-counterfeit label based on the laser-induced perovskite quantum dot microarray, which is disclosed in claim 7, is characterized in that in the step 3, the femtosecond laser parameters are that the single pulse energy is 0.05-1 mu J, the scanning speed is 50-600 mu m/s, the pulse width is 10-100 fs, and the NA of an objective lens is more than or equal to 1.4; The double-beam single-pulse energy is respectively 0.05-0.3 mu J and 0.5-1.5 mu J, and the micro-nano grating period is regulated gradually at 100-500 nm.
  10. 10. The method for preparing the anti-counterfeiting label based on the laser-induced perovskite quantum dot microarray, which is characterized in that in the step 5, the vacuum degree of vacuum drying at room temperature is 0.05-0.1 MPa, and the time is 1-2 hours; The flexible transfer adopts low-power femtosecond laser stripping and vacuum adsorption, the single pulse energy of the laser is 0.03-0.1 mu J, and the transfer precision is +/-0.1 mu m.

Description

Anti-counterfeiting label based on laser-induced perovskite quantum dot microarray and preparation method thereof Technical Field The invention relates to the technical field of anti-counterfeit labels, in particular to an anti-counterfeit label based on a laser-induced perovskite quantum dot microarray and a preparation method thereof. Background The perovskite quantum dots (PeQDs) have become research hot spots of novel anti-counterfeiting materials due to excellent performances of high fluorescence quantum yield, adjustable emission wavelength and the like, but in practical application, the performance of the anti-counterfeiting label is still limited by key technical bottlenecks, and the core requirements of high anti-counterfeiting grade, high resolution and environmental protection of high-end products are difficult to meet. The conventional process such as ink-jet printing and photoetching is adopted in the patterning preparation of the prior PeQDs-based anti-counterfeit label, the resolution is difficult to break through submicron, high-precision secret anti-counterfeit cannot be realized, the viscosity of PeQDs precursor is inaccurate to regulate and control, the substrate is not subjected to targeted hydrophilic-hydrophobic modification, so that the uniformity of the microarray is poor, the microarray is loosely combined with the substrate and easily falls off, meanwhile, the suitability of the flexible substrate is insufficient, the high resolution and the flexible application scene are difficult to be considered, an effective grading regulation and control system is not formed in the conventional laser induction process, and the preparation precision and efficiency are further restricted. In the aspect of anti-counterfeiting performance, the conventional label is mostly dependent on a single fluorescent color to realize anti-counterfeiting, the anti-counterfeiting dimension is deficient and easy to imitate, the accurate partition of different components PeQDs, the fluorescence service life and the multiple regulation and control of the polarization are not realized, the synchronous preparation and the accurate coordination of the PeQDs microarray and the micro-nano physical anti-counterfeiting structure are not realized, the anti-counterfeiting grade is difficult to promote, meanwhile, the label lacks the design of environment irreversible response and cannot be naturally degraded, the risk of secondary utilization exists, and the development trend of green environment protection is not met. Notably, the lack of synchronization of laser-induced PeQDs in-situ crystallization and micro-nanostructure preparation in the prior art and the formation of an adapted coordinated precursor viscosity and laser parameters regulation scheme further aggravates the above-described technical pain. In conclusion, the prior art is difficult to break through the bottleneck of submicron resolution, lacks multi-dimensional collaborative anti-counterfeiting design, has insufficient environmental protection and irreversibility, and can not meet the core requirements of high-end products. Therefore, the application provides an anti-counterfeit label based on a laser-induced perovskite quantum dot microarray and a preparation method thereof. Disclosure of Invention The invention aims at solving the problems that the prior art lacks a scheme for synchronously preparing laser-induced perovskite quantum dot micro-arrays and synergetic regulation and control of a precursor and laser parameters, and cannot meet the requirements of high anti-counterfeiting grade, high resolution and green environment protection of high-end products. The technical scheme of the invention is that the anti-counterfeit label based on the laser-induced perovskite quantum dot microarray comprises a substrate, a perovskite quantum dot microarray, a composite micro-nano structure, a flexible transition layer and an ultrathin protective layer; the flexible transition layer covers the surface of the perovskite quantum dot microarray, the ultrathin protective layer covers the surface of the flexible transition layer, a perovskite quantum dot precursor residual curing layer is arranged between the perovskite quantum dot microarray and the substrate; the perovskite quantum dot microarray is of a submicron structure, perovskite quantum dot precursors are prepared on the substrate for in-situ crystallization, and the perovskite quantum dot microarray is formed by perovskite quantum dot partitions with different components; The composite micro-nano structure and the perovskite quantum dot microarray are prepared synchronously to form the deep anti-counterfeiting structure. Optionally, the substrate is a rigid substrate or a flexible substrate, wherein the rigid substrate is one of glass and quartz, and comprises the raw materials of, by weight, 10-15% of SiO 260~75wt%、Al2O3, 5-8% of CaO, 2-5% of MgO and 0.3-1.0 mm; the flexible substrate is one of PET and PI,